Cof-substituted-n-trifluoromethyl-phenylsulfenamides



United States Patent O F 4 ,31 Int. Cl. C07c 101/48, 63/12 US. Cl.260-544 7 Claims ABSTRACT OF THE DISCLOSURE COF substituted Ntrifluoromethyl-phenylsulfenamides are obtained by the reaction offiuorocarbonyl-N- trifluorornethyl anilines with sulphenic acid halidesin the presence of a tertiary organic base.

BACKGROUND OF THE INVENTION Field of the invention The invention relatesto the production ofCOF-substituted-N-trifluoromethyl-phenylsulfenamides by reactingfiuorocarbonyl-N-trifluoromethyl-anilines with a sulphenic acid halidein the presence of a tertiary organic base.

Description of the prior art As shown by our earlier disclosureN-trifiuoromethylarylamines can be reacted with sulphenic acid halidesin the presence of tertiary nitrogen bases as acid acceptors to formN-trifiuoromethylated sulphenamides (German patent specification1,161,262).

SUMMARY OF THE INVENTION The invention lies in a process for theproduction of novel N-trifluoromethylated sulphenamides by reactingfiuoro carbonyl-N-trifiuoromethylanilines of the formula CFs (R011 inwhich:

n is an integer of from 1 to 4 and R represents a hydrogen or halogenatom or. a nitro, alkyl, alkoxy or trifiuoromethyl group in the presenceof a tertiary organic base as acid acceptor, with a sulphenic acidhalide of the formula R -SX in which:

R represents an alkyl radical which may be substituted with a halogenatom, an aryl radical which may be substituted with halogen atoms oralkyl or nitro groups and R further represents a chlorine atom or agroup SCI, and

X represents a chlorine or bromine atom.

DETAILED DESCRIPTION OF THE "INVENTION When R is halogen this ispreferably fluorine, chlorine, or bromine, and when it is an alkoxyoralkyl radical these are preferably lower aliphatic radicals having 1 to4 carbon atoms.

The alkyl radical R which may be substituted with up to 3 halogen atoms,which may be same or different, (preferably fluorine or chlorine)preferably have 1 to 4 carbon atoms, and the optionally substituted (onesub- 3,547,992 Patented Dec. 15, 1970 stituent up to completesubstitution) aryl radical (preferably phenyl or naphthyl) preferablycontains as its halogen atom substitutent fluorine, chlorine or bromineand as its alkyl group substitutent one which has 1 to 4 carbon atoms.

The fiuorocarbonyl-N-trifluoromethylanilines used as starting compoundsmay be obtained e.g. in accordance with German patent specification1,170,414. The following are examples of starting compounds used for theprocess:

3- or 4-fluorocarbonyl-N-trifluoromethylaniline,2-fluorocarbonyl-5-chloro-N-trifluoromethylaniline;3-fiuorocarbonyl-5-nitro-N-trifluoromethyl aniline;3-fluorocarbonyl-6-chloro-N-trifluoromethylaniline; and3-nitro-4-fluorocarbonyl-N-trifluoromethylaniline.

Sulphenic acid halides used for the process are also known. In additionto SCl and S Cl the following compounds may be mentioned as examples:Methylsulphene chloride, chloromethane sulphene chloride, butylsulphenechloride, perchlorornethylmercaptan, fiuorodichloromethanesulphenechloride, phenylsulphenechloride, phenylsulphene-bromide, 4-chloroor-bromoor -fluoro-phenylsulphenechloride, 2,4-dichlorophenylsulphenechloride, pentachlorophenylsulphene chloride, 2chloro-4-nitrophenylsulphene chloride, 2- or 4 nitrophenyl sulphenechloride, 2-, 3- or 4-methylphenylsulphene chloride or 2-chloro-l-naphthyl-sulphene chloride.

Apart from these specifically named compounds, the process according tothe invention may also be carried out with sulphenic acid chlorideswithin the definition given above, such as those known e.g. from thefollowing publications: Berichte der Deutschen Chernischen Gesellschaft,e.g. 58, pps. 409-416 (1925), and 84, pps. 911-916 (1961); ChemicalReviews 39, pp. 269-332 (1946).

The process according to the invention is explained below by way ofexample with reference to the reaction of3-fluorocarbonyl-N-trifiuoromethylaniline with fluorodichloromethanesulphene chloride:

0 O F C O F (Tertiary organic amine) T E A lTTH C1SC C12]? 1TI-SCFO13 0F 0 F Generally, about the equimolar quantity of sulphenic acid halideis used per mol of arylamine. Accordingly, only about /2 mol of SCl or 831 is used in the reaction per mol of arylamine. The tertiary organicamine used as acid acceptor is accordingly used in at least equirnolarquantity so that there is at least one mol available per mol of hydrogenhalide liberated in the reaction. The acid acceptor may also be used inan excess of up to about 30%.

Examples of suitable tertiary organic amines are triethylamine, pyridineor pyridines substituted by lower alkyl radicals, quinoline anddimethylbenzylamine.

The process according to the invention is carried out in the temperaturerange of about 0 to 50 C., preferably 20 to 40 C., advantageously in thepresence of an inert organic solvent such as methylene chloride,chloroform, benzene, chlorobenzene or dioxane. The products are workedup in the usual manner.

It must be regarded as distinctly surprising that the process accordingto the invention leads in a smooth reaction to high yields of the novelcompounds in spite of the presence of a GOP group, since, as is wellknown, N- trifluoromethyl sulphenamides are easily decomposed at theNS-bond by acylating agents (see Journal of Organic Chemistry 26, 3451(1961)).

3 Further, it is surprising that the new compounds are extremely heatstable and can therefore be distilled without decompostion and withoutside reactions in spite of the presence of the fluorocarbonyl group. Thenew sulphenic acid amides can be used as plant protective agents withinsecticidal and fungicidal action and as intermediate products forfurther reactions.

The fungicidal activity is demonstrated by applying the following newsulphenic acid amides:

COF

W=II, O1, CH3 W N 8-0 F 012 F3 Each of these compounds is applied in aconcentration of 50 ppm. (dissolved in acetone), and the growth of thefollowing fungi is completely inhibited (agar plate test):

Fungus: P a

Piricularia oryzae Rice. Cercospora musae Banana. Cercospora personataPeanut.

Also the other compounds obtainable according to the described processcan be used for the same purposes and show comparable activity.

EXAMPLE 1 55 g. triethylamine are added dropwise at room temperature toa solution of 103.5 g. 3-fluorocarbonyl-N- trifluoromethyl aniline and85 g. fiuorodichloromethane sulphene chloride in 200 ml. benzene, andthe reaction temperature is allowed to rise to 40 C. When the exothermicreaction has subsided, the reaction mixture is stirred for about anotherminutes, triethylamine hydrochloride is removed by suction filtrationand the solution in benzene is concentrated by evaporation in vacuo. Bysubsequent distillation, 136 g. of N-trifluoromethylated sulphenamide ofthe formula B.P. 145-450 C./20 mm. Hg

! H i /l GOF B.P. BIO-145 C./15 mm, Hg

OOF

HP. 142'147 C./l3 mm. Hg

OCH;

I N-SCFOlg I COF Bl. 160167 C./l3 mm. Hg

EXAMPLE 2 In a manner analogous to Example 1, 108 g. of theN-trifiuoromethylated sulphenamide of the formula CFa of BF. 123l28C./11 mm. Hg are obtained from 98 g.4-fluorocarbonyl-N-trifluoromethylaniline and g.fluorodichloromethanesulphenic acid chloride.

The following compounds are obtained in an analogous manner:

| COF B.P. 138145 c. 17 mm. Hg

EXAMPLE 3 45 g. dimethylbenzylamine are added dropwise to a solution of69 g. 2-flu0rocarbonylN-trifluoromethylaniline and 56.5 g.fiuorodichloromethane sulphenic acid chloride in 250 ml. benzene in sucha way that the internal temperature is maintained at 30 C. The mixtureis then stirred for about 30 minutes, separated from the amine salt bysuction filtration, and the filtrate is concentrated by distillation invacuo. 77 g. of trifluoromethylated sulphenamide of the formula NS G FCl:

B.P. 132136 C./13 mm. Hg; m): 1.4929

is obtained.

The following compounds are obtained in an analogous manner:

OOF

NS C C13 BI. Dis-151 "(l/13 mm. Hg

COF

i CF3 BI. 116-124 C./13 mm Hg Bl. 157-162" C./1l mm. Hg2-fluor0carbonyl-N-trifluoromethylaniline is obtained as follows:

750 ml. anhydrous hydrofluoric acid are placed in a stainless steelreaction vessel equipped with stirrer, reflux cooler and gas dischargetube. With the internal temperature at about 0 C., 500 g.2-trichloromethylphenylisocyanate (B.P. 138 C./10 mm. Hg, n :1.5872) arerun into the acid in the course of 3 hours, rapid evolution of HCltaking place. When the Whole quantity has been added, the reactionmixture is slowly heated to a temperature of 20 C., and worked up bydistillation after evolution of HCl has ceased,

274 g. (63% of the theory) of 2-fiuorocarbony1-N-trifiuoromethylanilineof HP. 70 to 72 C./16 mm. Hg, n :1.47O5 are obtained.

We claim:

1. COF-substituted-N-trifiuoro-methylated-phenyl sulfenamides of theformula COF in which R stands for hydrogen or a halogen atom selectedfrom the group consisting of floro, chloro and bromo, alkylor alkoxygroup having from 1 to 4 carbon atoms, a trifluoro methyl and a nitrogroup, R stands for CX wherein X is a halogen.

2. A COF-substituted-N-trifiuoro methylated phenylsulfenamide, accordingto claim 1, wherein X constitutes at least one member selected from thegroup consisting of fiuoro, chloro, and bromo.

3. A COF-substituted-N trifiuoromethylated phenylsulfenamide accordingto claim 1 having the following formula:

4. A COF-substituted-N-trifiuoromethylated-phenylsulfenamide accordingto claim 1 having the following formula:

5. A COF-substituted-N-trifluoromethylated-phenylsulfenamide accordingto claim 1 having the following formula:

6. A COF-substituted-N trifinoromethylated phenylsulfenamide accordingto claim 1 having the following formula:

sulfenamide according to claim 1 having the following formula:

COF

References Cited UNITED STATES PATENTS 3,236,842 2/1966 Klauke et a1260247.1

LORRAINE WEINBERGER, Primary Examiner E. J. GLEIMAN, Assistant ExaminerUS. Cl. X.R. 424?rl7 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent 547 ,992 Dated December 15 1970 Erich Klauke et a1.Inventor(s) It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

- Col. 5 first formula (Spec p. 7; 4th formula) tn i If S ICl Col. 5,second formula (Spec. 7, 5th formula) COF -co&' f Jen should be c1H-SCCl Signed and sealed this 27thdaj of April 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E.- SCHUYIER,. Attesting OfficerCommissions; g; zaps

